A chemically initiated adaptation of the classic [Ru(bipy)(3)](2+)/oxalate electrochemiluminescence coreactant system has revealed the elusive radical intermediates of the light-producing pathway. Oxalyl (HC(2)O(4)˙) and hydroxyformyl (HCO(2)˙) radicals have been captured on a quartz surface and characterised using EPR spectroscopy.

We show that latent oxalyl thioester surrogates are a powerful means to modify peptides and proteins in highly dilute conditions purified aqueous media or mixtures as complex cell lysates. Designed be shelf-stable reagents, they can activated on demand enable ligation reactions withpeptide concentrations low few hundred nM at rates approaching 30 M-1 s-1.

Recently, Roht et al. [J. Contam. Hydrol., 2013, 145, 10-16] observed that the presence of suspended non-Brownian macroscopic particles decreased the dispersivity of a passive solute, for a pressure-driven flow in a narrow parallel-plate channel at low Reynolds numbers. This result contradicts the idea that the streamline distortion caused by the random diffusive motion of the particles increas...

A new compound, bis[2-(methoxycarbonyl)phenyl]oxalate, made from methyl salicylate (oil of wintergreen) was found to be an excellent replacement for the typical halogen or nitro substituted oxalate esters used in peroxyoxa!ate chemiluminescence demonstrations. The compound is easily prepared and has good solubility in organic solvents such as ethy l acetate which is an environmentally friendly ...

Phosphoenolpyruvate phosphomutase (PEP mutase) from Tetrahymena pyriformis catalyzes the rearrangement of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr). A spectrophotometric P-pyr assay consisting of the coupled actions of P-pyr decarboxylase, phosphonoacetaldehyde hydrolase, and alcohol dehydrogenase was devised to monitor mutase catalysis. The reaction constants determined for PEP mu...

Oxalyl-tethered pyrroles can be doubly bridged with two difluoroboron chelating units to yield bright orange dyes. Interestingly, in polar organic solvents, the addition of fluoride and cyanide result in reversible detachment of the otherwise stable difluoroboron bridges, resulting in sharp changes in color. Thus, this novel compound behaves as a highly selective chromogenic sensor for fluoride...

Based on the mechanism postulated for the formation of the cyclic carbonates 3 in the reactions of glycols 1 with oxalyl chloride in the presence of triethylamine, we present here three efficient syntheses of the cyclic oxalates 2 of various glycols 1 by controlling the formation of 3: replacement of the base by pyridine markedly diminishes yields of 3 in all reactions, realizing dramatic rever...

New step-growth graft block copolymers were synthesized. These two-sided comb copolymers consisted of a poly(amic ester) (PAE) backbone and pendant poly(propylene oxide) (PPO) grafts. The copolymers were made via a macromonomer approach, in which the 4,6-bischlorocarbonyl isophthalic acid bis[poly(propylene oxide)] ester macromonomer was synthesized through the reaction of hydroxyl-terminated P...

Subsequent treatment of H2TPP(CO2H)4 (tetra(p-carboxylic acid phenyl)porphyrin, 1) with an excess of oxalyl chloride and HNR2 afforded H2TPP(C(O)NR2)4 (R = Me, 2; iPr, 3) with yields exceeding 80%. The porphyrins 2 and 3 could be converted to the corresponding metalloporphyrins MTPP(C(O)NR2)4 (R = Me/iPr for M = Zn (2a, 3a); Cu (2b, 3b); Ni (2c, 3c); Co (2d, 3d)) by the addition of 3 equiv of a...